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拥挤环境下的双分子化学反应

Bimolecular chemical reactions in crowded environments

  • 摘要: 利用二维朗之万动力学模拟研究了拥挤环境下的双分子化学反应.研究发现平均反应时间τ的分子拥挤剂面积分数依赖性取决于改变的方式.当通过向体系中添加拥挤剂使改变,τ随的增大单调增加.而当体系中发生逾渗现象时,τ的增长速率大大提高.若通过调整体系尺寸大小来改变,由于拥挤效应主导的动力学区域和拥挤剂浓度主导的动力学区域间的竞争,τ随的增大出现极小值.此外,发现随着拥挤剂尺寸的增大,双分子反应速率加快.最后,模拟数据表明反应时间符合指数分布,且体系的拥挤程度不会改变这一分布模式.

     

    Abstract: Using two-dimensional Langevin dynamics simulations, we investigate the kinetics of the bimolecular chemical reactions in crowded environments. An important finding is that the dependence of the mean reaction time τ on the area fraction of crowders  relies on the manner of varying . Specifically, When  is increased by adding crowders into the circular domain, a monotonic increase in τ is observed. Moreover, the growth rate of τ becomes much faster once the percolation occurs in the system. As  is tuned by varying the radius of the circular domain R, τ has a minimum as a function of , which is a result of two distinct dynamical regimes, i.e., the crowding-dominated regime and the density-dominated regime. As the size of crowders becomes larger, the reaction process is found to be accelerated. Finally, we show that distributions of the reaction time obey the exponential ones, and the degree of crowding does not alter the distribution pattern.

     

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